CN111138471A - Thioacid radical end-capped mercaptosilane coupling agent and synthesis method and application thereof - Google Patents

Thioacid radical end-capped mercaptosilane coupling agent and synthesis method and application thereof Download PDF

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CN111138471A
CN111138471A CN201911305633.2A CN201911305633A CN111138471A CN 111138471 A CN111138471 A CN 111138471A CN 201911305633 A CN201911305633 A CN 201911305633A CN 111138471 A CN111138471 A CN 111138471A
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coupling agent
rubber
reaction
mercaptosilane coupling
compound
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王滨
贾维杰
刘峰
张丹
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Eve Rubber Institute Co ltd
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Eve Rubber Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Abstract

The invention belongs to a silane coupling agent, and particularly relates to a thioacid radical end-capped mercapto silane coupling agent, and a synthesis method and application thereof. The thioate end-capped mercaptosilane coupling agent has a structure shown in a formula (I). Thioacids of formula (I)The radical-blocked mercaptosilane coupling agent can enhance the interaction between a polymer and a filler, reduce the hysteresis loss of a rubber material, reduce the Payne effect of the rubber material, and improve the dispersibility of white carbon black, thereby reducing the oil consumption and the emission of carbon dioxide in the running process of a tire and enhancing the wear resistance of the tire.

Description

Thioacid radical end-capped mercaptosilane coupling agent and synthesis method and application thereof
Technical Field
The invention relates to a silane coupling agent, in particular to a thioacid radical end-capping mercapto silane coupling agent, a synthetic method and application thereof.
Background
White carbon black is an inorganic filler, which is the most important inorganic reinforcing filler following carbon black because of its excellent reinforcing property, and exhibits strong polarity and high surface energy because its surface is covered with a large amount of silicon hydroxyl groups. The rubber molecules are nonpolar as alkyl chains, and when the two are blended, phase interface separation is easy to generate due to thermodynamic incompatibility.
The silane coupling agent is a silane containing two groups with different chemical properties simultaneously, including an organic functional group and a hydrolyzable silicon functional group, and the general formula of the silane coupling agent can be expressed as Y-R-SiX3. Because the silane coupling agent molecules simultaneously have two functional groups which are organophilic and organophilic, the silane coupling agent can play a role of a molecular bridge, connect rubber molecules and white carbon black on an interface, increase the compatibility of the rubber molecules and the white carbon black, improve the dispersibility of the white carbon black, enhance the interaction of the white carbon black and the rubber, and achieve the purposes of improving the processability, the physical property and the dynamic property of the rubber. Silane coupling agents have been developed to date in the middle of the last century and are quite diverse, with hundreds of known structures. Silane coupling agents of novel structure have also been developed and reported as in recent years, such as the oligomer-type silane coupling agent Rheinfiat 1715 from Rheinchemie Rheinau, Germany; an oligomer silane coupling agent developed by Nippon shoku rubber company, having an average molecular weight of about 800; the subject group of the university of south China's Jade & Min professor grafts the silicon functional group and other functional groups of the rubber auxiliary agent segment together, and synthesizes the multifunctional silane coupling agent; several macromolecular silane coupling agents are combined on the subject of the Zhuqing increase professor of Shandong university in China and are used for improving the interaction between the silicon rubber and the white carbon black. Although development and research of novel silane coupling agents have been ongoing, only over twenty types of silane coupling agents are currently distributed in the market from the viewpoint of significance to actual industrial production, and the types of silane coupling agents that can be applied to different industrial fields are rare.
Sulfur-containing silane coupling agents are the most important class in the tire rubber industry, and can be roughly classified into three classes, namely mercaptoalkoxysilane coupling agents; one is bis (polysulfur-chain silane coupling agents) such as Si69, Si 75; still another class is thiocarboxylate-based silane coupling agents (also known as hindered mercaptosilane coupling agents NXT). The mercapto alkoxy silane coupling agent is easy to generate scorch in the processing process due to the high reactivity of the end mercapto group, so that the higher viscosity is caused, the processing and the forming are not favorable, and the application of the silane coupling agent is limited due to the unpleasant smell of the mercapto alkoxy silane coupling agent; due to higher atom economy, proper mixing temperature and final rubber viscosity of the bis (polysulfide chain silane coupling agent), the bis (polysulfide chain silane coupling agent) is the most widely used silane coupling agent at present, for example, Si69 exclusively takes the role of chelating head in the silane coupling agent for tires for a long time, the bis (polysulfide chain silane coupling agent) has multiple functions of a coupling agent, a vulcanizing agent, a lubricant, an anti-vulcanization reversion agent and the like, a longer and softer vulcanization crosslinking bond can improve the dynamic mechanical property of tire rubber, but Si69 easily causes rubber scorching in use; thiocarboxylate silane coupling agents were first discovered in the 21 st century, hydrogen on original mercapto group was replaced by carbonyl, reduced the reactivity of mercapto group, the mercapto group that is blocked is in the sub-active state, the group of blocking mercapto group can be taken off while sulfurizing, thus show the characteristic (US20040210001) that mercapto group participates in the rubber vulcanization, such as NXT can reach better effects compared with Si69 and Si75, such as reducing the sizing material viscosity, reduce the number of mixing stages, lower costs, improve the processing property of sizing material, improve the filler dispersion, improve the dynamic mechanical properties of sizing material, it is the better silane coupling agent for tire at present.
The thiocarboxylate silane coupling agent NXT can be regarded as that carbonyl carries out end capping treatment on the mercapto silane coupling agent at the end position, the silicon functional group of the coupling agent reacts with white carbon black in the mixing process to change the surface polarity of the white carbon black, the driving force of the agglomeration of the filler white carbon black is reduced, the filler-filler interaction is reduced, the filler agglomeration is inhibited, and the dispersibility of the filler is improved. However, since the conventional coupling agent does not exhibit an advantage in enhancing the interaction force between the filler and the polymer, for example, the C — S bond energy of a common alkyl group-linked C — S bond is about 305KJ/mol, and the C — S bond energy of (C ═ O) -S in NXT is about 320.1KJ/mol, the C — S bond is not easily opened under kneading conditions, so that such a silane coupling agent does not easily interact with the polymer, and the interaction force between the polymer and the filler is relatively weak. Therefore, in order to better enhance the interaction force between the polymer and the filler and simultaneously have no obvious damage to the processing performance of the rubber material, finally improve the dispersibility of the white carbon black in the rubber material, achieve the purposes of reducing the hysteresis loss of rubber and reducing the heat generation and energy loss in the running process of a tire, conceptionally design a plurality of high-activity end-capping functional groups, and graft the end-capping functional groups and the mercaptosilane coupling agent together to synthesize the novel silane coupling agent so as to improve the interaction force between the polymer and the filler, and the method has important significance.
Disclosure of Invention
In order to solve the problem that the silane coupling agent in the prior art cannot well improve the interaction between a polymer and a filler, the invention provides a thioate end-capped mercaptosilane coupling agent.
In order to solve the technical problems, the invention adopts the following technical scheme:
a thioate-terminated mercaptosilane coupling agent has a structure shown in formula (I):
Figure BDA0002322985700000021
wherein, R is1Is selected from C1-C18An alkyl, aryl or cycloalkyl group of (a); the R is2Is absent, or is selected from the group consisting of S atoms; the R is3Selected from S atom or O atom, said R4Is C1-C18An alkyl, aryl, cycloalkyl, alkenyl or alkynyl group of (a); the R is5、R6、R7At least one is a hydrolyzable chlorine, bromine, alkoxy or ester group, the others are selected from hydrogen, alkyl, aryl or cycloalkyl.
Preferably, the coupling agent may be selected from
Figure BDA0002322985700000031
Silane coupling agents having only one sulfur atom are capable of breaking only the C-S bond to generate a sulfur radical in order to enhance the polymer-filler interaction, such as the most commonly used (C ═ O) -S in NXT where the C-S bond energy is about 320.1KJ/mol, so that the C-S bond is difficult to open under compounding conditions, and thus the silane coupling agent does not readily interact with the polymer, and the interaction force between the polymer and the filler is relatively weak. In the development process, the inventors want to design a coupling agent capable of enhancing the polymer-filler interaction under the mixing condition, and finally screen out the coupling agent with S-S bonds through the synthesis and screening of various compounds, but not all the coupling agents containing S-S bonds can promote the polymer-filler interaction well. Finally, the inventors have surprisingly found that the presence of the characteristic structures (C ═ O) -S, (C ═ S) -S or S- (C ═ S) -S in the silane coupling agents, where carbonyl C ═ O and thiocarbonyl C ═ S are strongly electron withdrawing groups, the S — S bond can be more polarized, making the S — S bond more susceptible to bond scission, under the mixing conditions, more active sulfur free radicals can exist, the sulfur free radicals form chemical bonds with polymers in the mixing process, the polar hydrolysis end of the coupling agent forms chemical bonds with the filler, thereby enhancing the interaction between the polymer and the filler, promoting the dispersion of the filler, inhibiting the agglomeration of the filler, reducing the hysteresis loss of the rubber material, and reducing the energy loss generated by the continuous breaking and reconstruction of the network structure of the filler, thereby reducing the energy loss of the tire in the running process.
The invention also aims to provide a synthesis method of the thioate end-capped mercaptosilane coupling agent shown in the formula (I), wherein the thioate end-capped mercaptosilane coupling agent can be prepared by reacting thiocarboxylate or thiocarbonate compounds with sulfenyl chloride compounds corresponding to mercaptoalkylsilane.
Preferably, the molar ratio of the thiocarboxylate compound or the thiocarbonate compound to the sulfenyl chloride compound corresponding to the mercaptoalkylsilane is 1:1.0 to 1.2.
The invention provides a method for synthesizing a thioacid radical end-capped mercaptosilane coupling agent shown in formula (I), which comprises the steps of dissolving a thiocarboxylate compound or a thiocarbonate in an organic solvent under an inert gas atmosphere to prepare a reaction solution with the concentration of 0.5-0.8mol/L, dropwise adding a sulfenyl chloride compound corresponding to mercaptoalkylsilane into the reaction solution, reacting at room temperature with the magneton rotation speed of 500-800r/min and the reaction time of 6-12 h.
Preferably, after the reaction is finished, removing the solvent of the reaction system, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein the eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 200:1-10:1, thereby finally obtaining the target compound, namely the thioacid radical end-capped mercaptosilane coupling agent.
Finally, the invention also provides the application of the thioate end-capped mercaptosilane coupling agent shown in the formula (I) in rubber mixing or vulcanization, so as to improve the interaction force between rubber and a filler and reduce hysteresis loss.
Further, the thioacid radical end-capped mercaptosilane coupling agent is applied to raw rubber isoprene rubber or styrene-butadiene/butadiene rubber, mixed by a conventional mixing method, and vulcanized rubber is obtained after vulcanization.
The invention provides a thioacid radical end-capped mercaptosilane coupling agent shown as a formula (I), which can enhance the interaction between a polymer and a filler, reduce the hysteresis loss of a rubber material, reduce the Payne effect of the rubber material, and improve the dispersibility of white carbon black, thereby reducing the oil consumption and the emission of carbon dioxide in the running process of a tire and enhancing the wear resistance of the tire. The invention uses the nucleophilic substitution reaction of mono-thiocarboxylate or dithio-carboxylate or trithiocarbonate on sulfenyl chloride to realize the synthesis of the novel mono-thiocarboxylate or dithio-carboxylate or trithiocarbonate radical-terminated mercaptosilane coupling agent for the first time, and has the advantages of simple and safe operation, high synthesis efficiency and wide universality.
Detailed Description
The invention discloses a thioacid radical end-capped mercaptosilane coupling agent, a synthesis method and application thereof, and can be realized by appropriately improving process parameters by taking the contents of the coupling agent as reference by the technical personnel in the field. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
Example 1
Under the atmosphere of inert gas and nitrogen, 11.42g (0.1mol) of potassium thioacetate is dissolved in 150mL of dichloromethane in a 500mL Schlenk bottle to prepare a suspension with the concentration of 0.67mol/L, then the solution is placed in an ice water bath (0 ℃), 32.75g (0.12mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1.2:1, the rotation speed of magnetons is 500r/min, the reaction time is 8h, and the reaction progress is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 50:1-20:1, so as to obtain 20g of the compound. The coupling agent is characterized by a thioacid radical end-capping mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ3.81(q,J＝7.0Hz,6H),2.74(t,J＝7.3Hz,2H),2.43(s,3H),1.79-1.70(m,2H),1.22(t,J＝7.0Hz,9H),0.76-0.70(m,2H).13C NMR(150MHz,CDCl3) δ 195.25,58.58,41.82,28.98,22.78,18.44,9.64.ESI-MS:335.0762, calculated as (M + Na): 335.0783, respectively; the reaction formula is as follows:
Figure BDA0002322985700000051
the target compound, i.e., the thioacid radical end-capped mercaptosilane coupling agent prepared by the synthesis method, bis- (gamma-propyltriethoxysilane) (Si69) tetrasulfide and 3-thiooctanoate-1-propyltriethoxysilane (NXT) are applied to the crude rubber isoprene rubber, the conventional mixing method and formula (detailed in Table 1) are adopted for mixing and vulcanizing, and the corresponding rubber material is subjected to performance detection, wherein the detection result is shown in Table 2.
The common mixing process is carried out by three sections, wherein one section is to keep the temperature of the raw rubber isoprene rubber, the white carbon black and the silane coupling agent at 150 ℃ for 2 min; in the second stage, stearic acid, zinc oxide, protective wax and an anti-aging agent are added into the first-stage rubber compound to carry out mixing reaction, and the mixture is heated to 150 ℃; mixing the accelerant, the sulfur and the second-stage rubber compound to obtain final rubber compound in the third stage;
vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.
Table 1: IR mixing formula detail
Figure BDA0002322985700000052
The structures of the Si69 and the NXT are as follows:
Figure BDA0002322985700000053
Figure BDA0002322985700000061
TABLE 2 elastomeric compound/vulcanizate Properties measurements
Figure BDA0002322985700000062
Injecting: the Si69 stock data were all set to 100, and the other stock data were percentages of their true data to the Si69 true data.
the tan delta value can be used for representing the hysteresis loss of the rubber compound, the smaller the tan delta value is, the lower the hysteresis loss is, and the data in the table 2 show that the thioate-terminated mercaptosilane coupling agent obtained in the embodiment can improve the hysteresis loss of the isoprene rubber compound.
ΔG'(0.1％-25％)The value represents the Payne effect of the sizing material, and further reflects the dispersibility of the white carbon black in the sizing material, delta G'(0.1％-25％)The smaller the value is, the smaller the Payne effect is, and the better the dispersibility of the white carbon black is; data in Table 2 show that from Δ G'(0.1％-25％)The value data shows that the thioate end-capped mercaptosilane coupling agent obtained by the embodiment can reduce Payne effect of the sizing material and improve the dispersibility of white carbon black in the sizing material.
300 stretch/100 stretch, the bound gum content can characterize the polymer-filler interaction to a certain extent, generally speaking, the greater the 300 stretch/100 stretch, the higher the bound gum content, the stronger the polymer-filler interaction; the data in Table 2 show that the thioate-terminated mercaptosilane coupling agent obtained in this example can enhance the polymer-filler interaction and, to a certain extent, the wear resistance of the tire.
Mooney viscosity values can be used to characterize the processability of the compound, with higher Mooney viscosity values being more detrimental to the processing of the compound; the data in Table 2 show that the Mooney viscosity @100 ℃ data show that the thioate-terminated mercaptosilane coupling agent obtained in the example does not increase the Mooney viscosity of the rubber compound and hardly impairs the processability of the rubber compound.
The obtained thioate end-capped mercaptosilane coupling agent, bis- (gamma-propyltriethoxysilane) (Si69) tetrasulfide and 1-propyltriethoxysilane (NXT) are applied to raw styrene-butadiene/butadiene rubber, and the conventional mixing method and formula (detailed in Table 3) are adopted for mixing and vulcanization, and the corresponding rubber material is subjected to performance detection, and the detection results are shown in Table 4.
The mixing process is carried out in three stages, and in the first stage, raw rubber butylbenzene/butadiene rubber, white carbon black, a silane coupling agent, stearic acid, zinc oxide, protective wax and an anti-aging agent are subjected to heat preservation for 2min at the temperature of 150 ℃; in the second stage, the first-stage rubber compound is thermally treated to 150 ℃; and in the third section, mixing the accelerator, the sulfur and the second-section mixed rubber to obtain final rubber.
Vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 165 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.
TABLE 3 SBR/BR compounding recipe
Figure BDA0002322985700000071
TABLE 4 elastomeric compound/vulcanizate Properties measurements
Figure BDA0002322985700000081
Injecting: the Si69 stock data were all set to 100, and the other stock data were percentages of their true data to the Si69 true data.
The data in Table 4 show that tan delta values can be used to characterize the hysteresis loss of the compound, with lower tan delta values giving lower hysteresis losses. It can be seen from the tan δ value data that example 1 can improve the hysteresis loss of butylbenzene/butadiene rubber.
ΔG'(0.1％-25％)The value represents the Payne effect of the sizing material, and further reflects the dispersibility of the white carbon black in the sizing material, delta G'(0.1％-25%) the smaller the Payne effect and the better the white carbon black dispersion, from Δ G'(0.1％And the value data of-25%) shows that the thioate end-capped mercaptosilane coupling agent obtained in the embodiment can reduce Payne effect of the sizing material and improve the dispersibility of white carbon black in the sizing material.
The 300/100 elongation, bound gel content in the data of Table 4, characterizes the interaction of polymer and filler to some extent, in general, the greater the 300/100 elongation, the higher the bound gel content, and the stronger the interaction of polymer and filler; therefore, the two data show that the thioate end-capped mercaptosilane coupling agent obtained by the implementation can better enhance the interaction between the polymer and the filler and enhance the wear resistance of the tire to a certain extent.
Example 2
11.42g (0.1mol) of potassium thioacetate are dissolved in 125mL of tetrahydrofuran under an inert gas atmosphere of argon in a 250mL Schlenk flask,preparing a suspension with the concentration of 0.8mol/L, then placing the solution in an ice water bath (0 ℃), dropwise adding 30.02g (0.11mol) of triethoxysilylpropylsulfenyl chloride into the solution system, placing the solution to room temperature after dropwise adding, wherein the molar ratio is 1.1:1, the rotation speed of magnetons is 600r/min, the reaction time is 10h, and tracking the reaction process by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 50:1-20:1, so as to obtain 22g of the compound. The coupling agent is characterized by a thioacid radical end-capping mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ3.81(q,J＝7.0Hz,6H),2.74(t,J＝7.3Hz,2H),2.43(s,3H),1.79-1.70(m,2H),1.22(t,J＝7.0Hz,9H),0.76–0.70(m,2H).13C NMR(150MHz,CDCl3) δ 195.25,58.58,41.82,28.98,22.78,18.44,9.64.ESI-MS:335.0762, calculated as (M + Na): 335.0783, respectively; the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000091
example 3
Under the atmosphere of inert gas and nitrogen, 11.42g (0.1mol) of potassium thioacetate is dissolved in 200mL of toluene in a 500mL Schlenk bottle to prepare a suspension with the concentration of 0.5mol/L, then the solution is placed in an ice-water bath (0 ℃), 27.29g (0.1mol) of triethoxysilylpropyl sulfenyl chloride is dropwise added into the solution system, the solution is placed at room temperature after the dropwise addition, the molar ratio is 1:1, the rotation speed of magnetons is 800r/min, the reaction time is 12h, and the reaction progress is tracked through TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 50:1-20:1, so that 18g of the compound is obtained. The coupling agent is characterized by a thioacid radical end-capping mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ3.81(q,J＝7.0Hz,6H),2.74(t,J＝7.3Hz,2H),2.43(s,3H),1.79–1.70(m,2H),1.22(t,J＝7.0Hz,9H),0.76–0.70(m,2H).13C NMR(150MHz,CDCl3) δ 195.25,58.58,41.82,28.98,22.78,18.44,9.64.ESI-MS:335.0762, calculated as (M + Na): 335.0783, respectively; the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000092
example 4
Under the atmosphere of inert gas argon, 1.76g (0.01mol) of potassium thiobenzoate is dissolved in 15mL of dichloromethane in a 50mL Schlenk bottle to prepare a suspension with the concentration of 0.67mol/L, then the solution is placed in an ice water bath (0 ℃), 3.28g (0.012mol) of triethoxysilylpropylsulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1.2:1, the magneton rotating speed is 500r/min, the reaction time is 12h, and the reaction progress is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 100:1-10:1, so that 2.8g of the compound is obtained. The coupling agent is characterized by a thioacid radical end-capping mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ8.00(d,J＝7.4Hz,2H),7.64(t,J＝7.4Hz,2H),7.50(t,J＝7.4Hz,1H),3.93(q,J＝7.0Hz,6H),2.92(t,J＝7.3Hz,2H),1.99-1.89(m,2H),1.32(t,J＝7.0Hz,9H),0.90-0.81(m,2H).13C NMR(150MHz,CDCl3) δ 190.14,135.80,134.09,128.93,127.72,58.89,43.16,23.18,18.70,9.95.ESI-MS:397.0952, calculated as (M + Na): 397.0939, respectively; the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000101
example 5
Under an inert gas nitrogen atmosphere, 3.81g (0.05mol) of carbon disulfide was added dropwise to 80mL of tetrahydrofuran containing (0.05mol, 50mL of a 1M solution in tetrahydrofuran) ethylmagnesium bromide in a 250mL Schlenk flaskAnd stirring the solution of the pyran for reaction for 3 hours, wherein the molar ratio is 1:1. Then placing the reaction system in an ice water bath (0 ℃), dropwise adding 16.34g (0.06mol) of triethoxysilylpropylsulfenyl chloride into the solution system, placing the solution system to room temperature after dropwise adding, wherein the molar ratio is 1.2:1, the magneton rotating speed is 700r/min, the reaction time is 12h, and tracking the reaction process by TLC detection. Quenching reaction with saturated ammonium chloride solution after reaction, washing with extraction liquid saturated saline solution, drying with anhydrous sodium sulfate, removing solvent from organic phase, and performing column chromatography with 400 mesh silica gel powder, wherein eluent system is petroleum ether and ethyl acetate, and gradient elution polarity selection range is 100:1-10:1, to obtain 12g of compound. The coupling agent is characterized by a thioate end-capped mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the data is as follows:1H NMR(600MHz,CDCl3)δ3.80(q,J＝7.0Hz,6H),3.05(q,J＝7.2Hz,2H),2.71(t,J＝7.3Hz,2H),1.77-1.68(m,2H),1.34(t,J＝7.2Hz,3H),1.21(t,J＝7.0Hz,9H),0.76-0.65(m,2H).13C NMR(150MHz,CDCl3) δ 233.11,58.55,41.76,39.85,22.73,18.40,15.07,9.62 ESI-MS:365.0702, calculated as (M + Na): 365.0711, respectively; the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000102
example 6
A solution of phenylmagnesium bromide was prepared from 7.85g (0.05mol) bromobenzene and 1.22g (0.05mol) magnesium strips in a 250mL Schlenk flask under an inert atmosphere of nitrogen in an organic solvent of 80mL anhydrous tetrahydrofuran. 3.81g (0.05mol) of carbon disulfide is added into the phenylmagnesium bromide solution dropwise, and the reaction is stirred for 2.5h with the molar ratio of 1:1. Then the reaction system is placed in an ice water bath (0 ℃), 16.34g (0.06mol) of triethoxysilylpropylsulfenyl chloride is dripped into the solution system, the solution system is placed to the room temperature after the dripping, the molar ratio is 1.2:1, the magneton rotating speed is 600r/min, the reaction time is 10h, and the reaction process is tracked by TLC detection. Quenching reaction with saturated ammonium chloride solution after reaction, washing with saturated salt solution, drying with anhydrous sodium sulfate, removing solvent from organic phase, and separating by column chromatography with 400 mesh silica gel powderThe eluent system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 100:1-10:1, so that 13g of the compound is obtained. The coupling agent is characterized by a thioacid radical end-capping mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ8.02–7.80(m,2H),7.56–7.30(m,3H),3.90(q,J＝7.0Hz,6H),2.87(t,J＝7.3Hz,2H),1.95–1.85(m,2H),1.30(t,J＝7.0Hz,9H),0.86–0.76(m,2H).13C NMR(150MHz,CDCl3) δ 221.15,143.92,132.88,128.26,127.74,58.86,43.11,23.14,18.68,9.93.ESI-MS:413.0725, calculated as (M + Na): 413.0711, the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000111
example 7
6.21g (0.1mol) of ethanethiol are slowly added dropwise to a suspension of 5.61g (0.1mol) of potassium hydroxide in anhydrous ethanol (70mL) under ice-water bath conditions (0 ℃) in a 250mL Schlenk flask under an inert gas nitrogen atmosphere for more than 0.5h, and after completion, the mixture is left to react at room temperature for 1.5 h. Then placing the reaction system in an ice-water bath (0 ℃), slowly dropwise adding 7.61g (0.1mol) of carbon disulfide into the reaction system, placing the reaction system to room temperature after dropwise adding, continuing to react for 3 hours, and obtaining ethyl trithiocarbonate potassium salt through post-treatment, wherein the molar ratio of the ethyl trithiocarbonate potassium salt to the ethyl trithiocarbonate potassium salt is 1:1: 1.
Dissolving 10.58g (0.06mol) of newly prepared ethyl trithio potassium carbonate in 100mL of dichloromethane in a 250mL Schlenk bottle under the atmosphere of inert gas nitrogen to prepare a suspension with the concentration of 0.6mol/L, then placing the solution in an ice water bath (0 ℃), dropwise adding 19.65g (0.072mol) of triethoxysilylpropyl sulfenyl chloride into the solution system, placing the solution to room temperature after dropwise adding, wherein the molar ratio is 1.2:1, the rotation speed of magnetons is 800r/min, the reaction time is 12h, and the reaction progress is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 200-180:1, so as to obtain 16g of the compound. Warp beamThe nuclear magnetic resonance spectrum and the high-resolution mass spectrum are characterized by a thioate end-capped mercaptosilane coupling agent, and the characterization data are as follows:1H NMR(600MHz,CDCl3)δ3.81(q,J＝7.0Hz,6H),3.30(q,J＝7.2Hz,2H),2.96(t,J＝7.3Hz,2H),1.89–1.80(m,2H),1.36(t,J＝7.2Hz,3H),1.21(t,J＝7.0Hz,9H),0.79–0.70(m,2H).13C NMR(150MHz,CDCl3) δ 228.42,58.56,42.45,32.94,23.08,18.40,12.78,9.75 ESI-MS:397.0451, calculated as (M + Na): 397.0432, respectively; the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000112
example 8
9.46g (0.08mol) of n-hexylmercaptan was slowly added dropwise to a suspension of 4.49g (0.08mol) of potassium hydroxide in anhydrous ethanol (80mL) under ice-water bath conditions (0 ℃) in a 250mL Schlenk flask under an inert gas nitrogen atmosphere for more than 0.5h, and after completion, the mixture was left to react at room temperature for 1.5 h. Then placing the reaction system in an ice-water bath (0 ℃), slowly dropwise adding 6.09g (0.08mol) of carbon disulfide into the reaction system, placing the reaction system to room temperature after dropwise adding, continuing to react for 3 hours, and obtaining n-hexyl trithio potassium carbonate salt through post-treatment, wherein the molar ratio of the n-hexyl trithio potassium carbonate salt to the n-hexyl trithio potassium carbonate salt is 1:1: 1.
Under the atmosphere of inert gas nitrogen, 11.62g (0.05mol) of newly prepared n-hexyltrithiocarbonate is dissolved in 100mL of dichloromethane in a 250mL Schlenk bottle to prepare a suspension with the concentration of 0.5mol/L, then the solution is placed in an ice water bath (0 ℃), 15.01g (0.055mol) of triethoxysilylpropylsulfenyl chloride is dripped into the solution system, the solution is placed to the room temperature after the dripping, the molar ratio is 1.1:1, the rotation speed of magnetons is 600r/min, the reaction time is 10h, and the reaction progress is followed by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 200-180:1, so as to obtain 16g of the compound. The coupling agent is characterized by a thioacid radical end-capping mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ3.81(q,J＝7.0Hz,6H),3.27(t,J＝7.5Hz,2H),2.95(t,J＝7.3Hz,2H),1.88–1.79(m,2H),1.74–1.66(m,2H),1.45–1.37(m,2H),1.33–1.25(m,4H),1.21(t,J＝7.0Hz,9H),0.87(t,J＝7.0Hz,3H),0.78–0.70(m,2H).13C NMR(150MHz,CDCl3) δ 228.40,58.55,42.43,37.87,31.39,28.84,27.58,23.07,22.56,18.40,14.09,9.74.ESI-MS:453.1058, calculated as (M + Na): 453.1031, respectively; the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000121
example 9
11.02g (0.1mol) of thiophenol were slowly added dropwise to a suspension of 5.61g (0.1mol) of potassium hydroxide in absolute ethanol (90mL) under ice-water bath conditions (0 ℃ C.) under an inert gas nitrogen atmosphere over a period of more than 0.5h in a 250mL Schlenk flask, and after completion, the reaction was allowed to stand at room temperature for 1.5 h. Then placing the reaction system in an ice-water bath (0 ℃), slowly dropwise adding 7.61g (0.1mol) of carbon disulfide into the reaction system, placing the reaction system to room temperature after dropwise adding, continuing to react for 3 hours, and obtaining phenyl trithio potassium carbonate salt through post-treatment, wherein the molar ratio of the phenyl trithio potassium carbonate salt to the phenyl trithio potassium carbonate salt is 1:1: 1.
Under the atmosphere of inert gas and nitrogen, 11.22g (0.05mol) of newly prepared phenyl trithio potassium carbonate is dissolved in 80mL of dichloromethane in a 250mL Schlenk bottle to prepare a suspension with the concentration of 0.625mol/L, then the solution is placed in an ice water bath (0 ℃), 16.38g (0.06mol) of triethoxy silicon propyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1.2:1, the rotation speed of magnetons is 700r/min, the reaction time is 12h, and the reaction progress is tracked through TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 200-100:1, so as to obtain 15g of the compound. The coupling agent is characterized by a thioacid radical end-capping mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high resolution mass spectrum, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.52-7.15(m,5H),3.93(q,J＝7.0Hz,6H),3.13(t,J＝7.3Hz,2H),2.08–1.98(m,2H),1.31(t,J＝7.0Hz,9H),0.92–0.84(m,2H).13C NMR(150MHz,CDCl3) δ 231.22,135.73,132.90,131.26,129.95,58.86,43.77,23.45,18.66,10.05.ESI-MS:445.0455, calculated as (M + Na): 445.0432, respectively; the reaction formula of the above reaction is shown below:
Figure BDA0002322985700000131
the thioacid radical end-capped mercaptosilane coupling agent compound obtained in the embodiments 4 to 9 can enhance the interaction between the polymer and the filler, reduce the hysteresis loss of the rubber material, reduce the Payne effect of the rubber material, and improve the dispersibility of the white carbon black, thereby reducing the oil consumption and the emission of carbon dioxide in the running process of the tire, and enhancing the wear resistance of the tire, and the effect data are not repeated herein.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A thioate-terminated mercaptosilane coupling agent has a structure shown in formula (I):
Figure FDA0002322985690000011
wherein, R is1Is selected from C1-C18An alkyl, aryl or cycloalkyl group of (a); the R is2Is absent, or is selected from the group consisting of S atoms; the R is3Selected from S atom or O atom, said R4Is C1-C18An alkyl, aryl, cycloalkyl, alkenyl or alkynyl group of (a); the R is5、R6、R7At least one is a hydrolyzable chlorine, bromine, alkoxy or ester group, the others are selected from hydrogen, alkyl, aryl or cycloalkyl.
2. The thioester-blocked mercaptosilane coupling agent of claim 1, wherein the coupling agent is selected from the group consisting of
Figure FDA0002322985690000012
3. The method for synthesizing a thioate-terminated mercaptosilane coupling agent according to claim 1 or 2, wherein the thioate-terminated mercaptosilane coupling agent is obtained by reacting a thiocarboxylate compound or a thiocarbonate compound with a sulfenyl chloride compound corresponding to mercaptoalkylsilane.
4. The method of claim 3, wherein the molar ratio of said thiocarboxylate or thiocarbonate compound to the corresponding sulfenyl chloride compound of the mercaptoalkylsilane is from 1:1.0 to 1.2.
5. The synthetic method as claimed in claim 3, wherein the reaction is carried out by dissolving thiocarboxylate or thiocarbonate compound in organic solvent under inert gas atmosphere to obtain reaction solution with concentration of 0.5-0.8mol/L, adding mercaptoalkylsilane corresponding sulfenyl chloride compound dropwise into the reaction solution, reacting at room temperature with magneton rotation speed of 500-.
6. A synthesis method as claimed in claim 3 or 5, characterized in that, after the reaction is finished, the solvent of the reaction system is removed, and then column chromatography separation is carried out by using silica gel powder of 400 meshes, the eluant system is petroleum ether and ethyl acetate, the gradient elution polarity selection range is 200:1-10:1, and finally the target compound thioacid radical end-capped mercaptosilane coupling agent is obtained.
7. Use of the thioester-blocked mercaptosilane coupling agent of claim 1 in rubber compounding or vulcanization to increase the interaction force between rubber and filler to reduce hysteresis loss.
8. The use of claim 7, wherein: and (3) applying the thioacid radical end-capped mercaptosilane coupling agent to raw rubber isoprene rubber or butylbenzene/butadiene rubber, mixing, and vulcanizing to obtain vulcanized rubber.
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